By using X-ray photoelectron spectroscopy and IR spectroscopy．a series of coordination units of methyl acrylate (M) and 2-vinyl pyridine(V) copolymer rhodium complexes were studied in comparison with those of methyl acrylate (M) and 4-vinyl pyfidine(V’) copolymer rhodium complexes．The influence of the micmstmctures of their active centers and reaction temperature on their catalytic activity for methanol carbonylation was investigated by well-directed experiments．It has been found that the complexes containing methyl acrylate (M) and 2-vinyl pyridine (V) copolymer ligands exhibit much higher catalytic activity than those of methyl acrylate (M) and 4-vinyl pyridine (V’) copolymer rhodium complexes on carbonylation of methanol．It is suggested that the 2-substituted vinyl pyridine possesses the favored catalytic mierostructure for such reactions．These experimental observations provided theoretical and practical incentive to fuaher investigation．